Carbonyl containing compounds

ABSTRACT

In accordance with the present invention, there is provided a novel composition of matter having the formula:                    
     wherein R a , R b , R c , R d  and R e  are independently selected from the group consisting of H, alkyl groups and substituted alkyl groups having about 1 to 10 6  carbon atoms, alkenyl groups and substituted alkenyl groups having about 3 to 10 6  carbon atoms, wherein the substituents on the alkyl and/or alkenyl groups are selected from the group consisting of alkoxy, halogen, CN, OH, HO(CH 2 CH 2 O) x  (X=1-10), acyl, acyloxy and aryl substituents.

This is a divisional of application Ser. No. 09/233,010, filed Jan. 19,1999, now U.S. Pat. No. 6,077,915, which was a continuation of Ser. No.07/928,604, filed Aug. 26, 1992, which was a CIP of Ser. No. 07/556,244,filed Jul. 23, 1990, both abandoned.

FIELD OF THE INVENTION

The present invention relates to novel compounds formed from acycliccarbonyl compounds and unsaturated hydrocarbons.

BACKGROUND OF THE INVENTION

Various unsaturated hydrocarbon polymers have been reacted with maleicanhydrides to form a variety of maleic anhydride adducts of unsaturatedhydrocarbon polymers. The reactivity of maleic anhydride with manyunsaturated hydrocarbon polymers is poor and in some instances, as forexample with EPDM rubber, even employment of extensive heating isineffective. Free employment of extensive heating is ineffective. Freeradical reactions which graft maleic anhydride onto the unsaturatedhydrocarbon polymer have been utilized as alternative routes. Freeradical grafting leads to chain scission, crosslinking and solventgrafting if the solvent is sufficiently reactive. The reaction ofacyclic carbonyl monomers with the unsaturated hydrocarbon polymerovercomes these aforementioned deficiencies in that the acyclic carbonylmonomers can be reacted with the unsaturated hydrocarbon polymer atmoderate temperatures in either the bulk or solution state without theemployment of free radical initiators to form novel polymers which areuseful as solution viscosifiers.

SUMMARY OF THE INVENTION

In accordance with the present invention, there is provided a novelcomposition of matter having the formula:

wherein R_(a), R_(b), R_(c), R_(d) and R_(e) are independently selectedfrom the group consisting of H, alkyl groups and substituted alkylgroups having about 1 to 10⁶ carbon atoms, alkenyl groups andsubstituted alkenyl groups having about 3 to 10⁶ carbon atoms, whereinthe substituents on the alkyl and/or alkenyl groups are selected fromthe group consisting of alkoxy, halogen, CN, OH, HO(CH₂CH₂O)x (X=1-10),acyl, acyloxy and aryl substituents.

These novel compounds are formed by contacting a hydrocarbon having theformula:

with an acyclic carbonyl having the formula:

for a time and at a temperature sufficient to form the compounds, and inwhich R_(a), R_(b), R_(c), R_(d), R_(e), X and Y are as described aboveand Q=HOH, MeOH, EtOH, or n-BuOH; n=0,1,>1; X or Y are selected from thegroup consisting of —OH; —OR₁; NR₁R₂; R₁; wherein R₁ has about 1 toabout 18 carbon atoms,

wherein R₂ is hydrogen or any alkyl group of from about 1 to about 18carbon atoms, —NR₃R₄ wherein R₃ and R₄ are alkyl groups of from about 1to about 18 carbon atoms; OR₅ wherein R₅ is hydrogen or an alkyl grouphaving about 1 to about 18 carbon atoms, —COOR₆ wherein R₆ is hydrogenor an alkyl group having about 1 to about 18 carbon atoms, —CN, and —SR₇wherein R₇ is an alkyl group having about 1 to about 18 carbon atoms.Typical monomers are ketomalonic acid, esters of ketomalonic acidincluding alkyl and aryl esters; other useful keto-acids are alpha ketosuccinic acid, diketo succinic acid, and any alpha ketohydrocarboic acidand alpha, beta-diketohydrocarboic acids and their ester and amideanalogs which have a molecular weight of about 130 to 500. Usefulketones include dimethyl, diphenyl and di-tolyl tri- and tetraketones.

The compounds of the present invention are useful as solutionviscosification agents.

GENERAL DESCRIPTION

Compounds having the formula:

are prepared by contacting an olefinic compound and an acyclic carbonylcompound for a time and at a temperature sufficient to form thecompound. Thus, a typical reaction to produce these novel carbonylcompounds is represented by the equation:

wherein R_(a), R_(b), R_(c), R_(d) and R_(e) are independently selectedfrom the group consisting of H, alkyl groups and substituted alkylgroups having about 1 to 10⁶ carbon atoms, alkenyl groups andsubstituted alkenyl groups having about 3 to 10⁶ carbon atoms, whereinthe substituents on the alkyl and/or alkenyl groups are selected fromthe group consisting of alkoxy, halogen, CN, OH, HO(CH₂CH₂O)_(x)(X=1-10), acyl, acyloxy and aryl substituents. Q=HOH, MeOH, EtOH, orn-BuOH; n=0,1,>1; X or Y are selected from the group consisting of —OH;—OR₁; NR₁R₂; R₁; wherein R₁ has about 1 to about 18 carbon atoms,

wherein R₂ is hydrogen or any alkyl group of from about 1 to about 18carbon atoms, —NR₃R₄ wherein R₃ and R₄ are alkyl groups of from about 1to about 18 carbon atoms; OR₅ wherein R₅ is hydrogen or an alkyl grouphaving about 1 to about 18 carbon atoms, —COOR₆ wherein R₆ is hydrogenor an alkyl group having about 1 to about 18 carbon atoms, —CN, and —SR₇wherein R₇ is an alkyl group having about 1 to about 18 carbon atoms.Typical monomers are ketomalonic acid, esters of ketomalonic acidincluding alkyl and aryl esters; other useful ketoacids are alpha ketosuccinic acid, diketo succinic acid, and any alpha ketohydrocarboic acidand alpha, beta-diketohydrocarboic acids and their ester and amideanalogs which have a molecular weight of about 130 to 500. Usefulketones include dimethyl, diphenyl and di-tolyl tri- and tetraketones.

Especially preferred olefinic hydrocarbons are alkenes having from 8 to30 carbon atoms and olefinic polymers containing an allylic hydrogen andhaving molecular weights ranging from about 500 to about 10,000,000. Theolefinic hydrocarbons may, of course, be substituted withfunctionalities such as —CN, —OH, HO(CH₂CH₂O)_(x) (x=1-10), alkoxy,halogen, and

wherein W═C, N; V═O, S, SO₂; and X is selected from the group consistingof OH; —OR₁, NR₁R₂; R₁; wherein R₁ has about 1 to about 18 carbon atoms,

wherein R₂ is hydrogen or any alkyl and has about 1 to about 18 carbonatoms, —NR₃R₄ wherein R₃ and R₄ has about 1 to about 18 carbon atoms,OR₅ wherein R₅ is hydrogen or an alkyl group having about 1 to about 18carbon atoms, —COOR₆ wherein R₆ is hydrogen or an alkyl group havingabout 1 to about 18 carbon atoms, —CN and —SR₇, wherein R₇ is an alkylgroup having about 1 to about 18 carbon atoms. Typical substitutedalkenes include oleic acid, oleyl alcohol, methyl oleate, 2-octadecenylsuccinic anhydride, octadecenyl benzene, octadecenyl methyl ketone,octadecenyl phenyl sulfide, octadecenyl phenyl sulfone, octadecenylchloride, octadecenyl phenol, chlorobutyl, polyisobutenyl succinicanhydride, and related functional olefins and polyolefins.

Among the preferred polymers are butyl rubber and EPDM polymers. Theexpression “butyl rubber” as employed in the specification and claims isintended to include copolymers made from a polymerization reactionmixture having therein from 70 to 99.5% by weight of an isobutylene andabout 0.5 to 30% by weight of a conjugated multiolefin having from about4 to 14 carbon atoms, e.g., isoprene. The resulting copolymer contains85 to 99.8% by weight of combined isoolefin and 0.2 to 15% of combinedmultiolefin.

Butyl rubber generally has a Staudinger molecular weight as measured byGPC of about 20,000 to about 500,000, preferably about 25,000 to about400,000, especially about 100,000 to about 400,000 and a Wijs Iodine No.of about 0.5 to 50, preferably 1 to 15. The preparation of butyl rubberis described in U.S. Pat. No. 2,356,128, which is incorporated herein byreference.

For the purposes of this invention, the butyl rubber may haveincorporated therein from about 0.2 to 10% of combined multiolefin;preferably about 0.5 to about 6%, more preferably about 1 to about 4%,e.g., 2%.

Illustrative of such a butyl rubber is Exxon butyl 365 (Exxon ChemicalCompany), having a mole percent unsaturation of about 2.0% and a Mooneyviscosity (ML, 1+3, 212° F.) of about 40 to 50.

Low molecular weight butyl rubbers, i.e., butyl rubbers having aviscosity average molecular weight of about 5,000 to 85,000, and a molepercent unsaturation of about 1 to about 5%, may be sulfonated toproduce the polymers useful in this invention. Preferably, thesepolymers have a viscosity average molecular weight of about 25,000 toabout 60,000.

The EPDM terpolymers are low unsaturated polymers having about 0.5 toabout 10.0 wt. % olefinic unsaturation, more preferably about 2 toabout,8, most preferably about 3 to 7 defined accordingly to thedefinition as found in ASTM-1418-64 and is intended to mean terpolymerscontaining ethylene and propylene in the backbone and an olefin residuein the side chain as a result of multiolefin incorporation in thebackbone. Illustrative methods for producing these terpolymers are foundin U.S. Pat. No. 3,280,082, British Patent No. 1,030,289 and FrenchPatent No. 1,386,600, which are incorporated herein by reference. Thepreferred polymers contain about 40 to about 75 wt. % ethylene and about1 to about 10 wt. % of a diene monomer, the balance of the polymer beingpropylene. Preferably, the polymer contains about 45 to about 70 wt. %ethylene, e.g., 50 wt. % and about 2.6 to about 8.0 wt. % diene monomer,e.g., 5.0 wt. %. The diene monomer is preferably a nonconjugated diene.

Illustrative of these nonconjugated diene monomers which may be used inthe terpolymer (EPDM) are 1,4-hexadiene, dicyclopentadiene,4-ethylidene-2-norbornene, 5-methylene-2-norbornene,5-propenyl-norbornene, methyl tetrahydroindene and4-methyl-methylene-2-norbornene.

A typical EPDM is Vistalon 2504 (sold by Exxon Chemical Company,Houston, Tex.), a terpolymer having a Mooney viscosity (ML, 1+8, 212°F.) of about 40 and having an ethylene content of about 50 wt. % and a5-ethylidene-2-norbornene content of about 5.0 wt. %. The M_(n) asmeasured by GPC of Vistalon 2504 is about 47,000, the M_(v) as measuredby GPC is about 145,000 and the M_(w) as measured by GPC is about174,000.

Another EPDM terpolymer Vistalon 2504-20 is derived from Vistalon 2504(also sold by Exxon Chemical Company) by a controlled extrusion process,wherein the resultant Mooney viscosity at 212° F. is about 20. The Mn asmeasured by GPC of Vistalon 2504-20 is about 26,000, the M_(v) asmeasured by GPC is about 90,000 and the M_(w) as measured by GPC isabout 125,000.

Nordel 1320 (sold by Dupont, Wilmington, Del.) is another terpolymerhaving a Mooney viscosity at 212° F. of about 25 and having about 53 wt.% of ethylene, about 3.5 wt. % of 1,4-hexadiene, and about 43.5 wt. % ofpropylene.

The EPDM terpolymers of this invention have a number average molecularweight (M_(n)) as measured by GPC of about 10,000 to about 200,000, morepreferably of about 15,000 to about 100,000, most preferably of about20,000 to about 60,000. The Mooney viscosity (ML, 1+8, 212° F.) of theEPDM terpolymer is about 5 to about 60, more preferably about 10 toabout 50, most preferably about 15 to about 40. The M_(v) as measured byGPC of the EPDM terpolymer is preferably below about 350,000 and morepreferably below about 300,000. The M_(w) as measured by GPC of the EPDMterpolymer is preferably below about 500,000 and more preferably belowabout 350,000.

Other suitable olefin polymers having M_(n) of about 500 to 10⁶ includepolymers comprising a major molar amount of C₂ to C₅ monoolefins, e.g.,ethylene, propylene, butylene, isobutylene and pentene. The polymers maybe homopolymers such as polyisobutylene, as well as copolymers of two ormore such olefins such as copolymers of ethylene and propylene, butyleneand isobutylene, propylene and isobutylene and the like.

The reaction of the acyclic carbonyl compound with the olefiniccontaining compound can occur in solution, in a melt and in polymerprocessing equipment such as a rubber mill, a Brabender, an extrude or aBanbury mixer.

Ene adductions can also be effected with acid catalysts such as kaolin,montmorillonite, silicates, SnCl₄, FeCl₃, and BF₃, which facilitateadduct formation. Moreover, the acid catalysts can produce lactones,secondary ene adducts and cyclic ethers, the product ratios varying withreaction conditions, and catalyst and reactant types.

The time and temperature for contacting can be varied widely and willdepend, in part, on whether a catalyst is present. In general, theacyclic carbonyl compound is contacted with the olefinic containingcompound in solution at temperatures ranging from about 50° C. to about220° C. for times ranging from about 4 to about 40 hours.

Typically, the olefinic compound is dissolved in a suitable solvent,such as tetrahydrofuran, xylene or mineral oil and heated totemperatures ranging from about 50° C. to about 220° C. The carbonylcompound, as a hydrate or hemiketal of methanol, butanol, or a suitablealcohol, is dissolved in a suitable solvent such as tetrahydrofuran,dioxane, or butanol, and added to the heated olefin solution. Thereaction mixture is heated, with stirring, until infrared and NMRanalysis of the mixture indicates that the ene-addition of the carbonylmonomer to the unsaturated polymer is complete. Depending on temperatureand concentration, reaction periods of about 4 to 40 hours aresufficient to achieve high conversions to mono- and/or multiple eneadducts.

Optionally, bulk reactions can be carried out at about 80° C. to about200° C. for approximately 3 to 300 minutes, depending upon thepolyolefin used, the carbonyl compound reactivity, and use of acatalyst.

If necessary, products can be isolated by solvent removal byevaporation, or by adding the reaction mixture to a polar solvent suchas acetone, which induces the precipitation of the functionalizedpolymer.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The following examples illustrate the present invention without,however, limiting the same hereto.

EXAMPLE 1

A mixture of diethyl ketomalonate (6.12 g) and 1-octadecene (8.84 g) wascombined in a reaction flask magnetically stirred and heated to 160-170°C. for 3 hours. The temperature was raised to 200° C. and kept at 200°C. for 30 hours. Upon cooling, the reaction mixture solidified. Thesolids, recrystallized from diethyl ether, showed a mass spectrum with amolecular ion (426) and an infrared spectrum with a strong hydroxylabsorption band at 3 microns, and a very strong ester carbonyl band at5.82 microns. The CMR spectrum of the eneadduct featured olefinic andester carbon signals consistent with the proposed structure (A):

EXAMPLE 2

One hundred grams of polyisobutylene, MW 950, and 34.0 grams of diethylketomalonate were combined in a reaction flask, stirred magnetically,and heated at 200° C. for about 40 hours. Rotoevaporation of thereaction mixture at about 100° C. for 8 hours afforded a residue whichfeatured (a) an infrared spectrum with a strong ester carbonylabsorption band at 5.85 microns, and (b) a saponification number of 92.

EXAMPLE 3

One hundred grams of polyisobutylene succinic anhydride (MW ⁻1050)having a saponification number of 55 were combined with 17 grams ofdiethyl ketomalonate, and heated to about 200° C. for 48 hours.

Rotoevaporation of the reaction mixture at about 100° C. for 8 hoursgave a residue which featured an infrared spectrum having anhydride andester carbonyl absorption bands at 5.65 and 5.85 microns, respectively.

EXAMPLE 4

A mixture of 95 grams of polyisobutylene (MW⁻950), 10 grams of maleicanhydride, and 17.4 grams of diethyl ketomalonate was heated at about210° C. for 40 hours. The cooled reaction mixture was dissolved in 500ml of cyclohexane, filtered and rotoevaporated at about 100° C. for 8hours. The residue featured an infrared spectrum with strong anhydride,and ester carbonyl absorption bands at 5.65 and 5.85 microns,respectively.

EXAMPLE 5

Ten grams of Vistalon-7504, an ethylidene norbornene (ENB) terpolymercontaining about 52% ethylene, 43% propylene and 5% ENB, and having aMn⁻55,000, were dissolved in 100 ml of xylene containing 4 grams ofdiethyl ketomalonate. The mixture was heated to about 135° C. andmaintained at 135° C. for about 30 hours under a blanket of nitrogen.Addition of the cooled reaction mixture to one liter of acetone causedthe functionalized polymer to precipitate from solution. The driedpolymer analyzed for 5.04% oxygen, and featured an infrared spectrum(film) with an intense ester carbonyl band at 5.82 microns, consistentwith ene adducts including structure (B) shown below:

What is claimed is:
 1. A composition formed by contacting an olefinicpolymer containing an allylic hydrogen and having a molecular weightfrom about 500 to 10,000,000 with an acyclic carbonyl of the formula:

wherein Q is HOH, MeOH, EtOH or n-BuOH; n is 0,1 or >1; and X and Y areindependently selected from the group consisting of: —OH, —OR₁, NR₁, R₂,—R₁ and phenyl; wherein R₁ is an alkyl group, having about 1 to about 18carbon atoms, and R₂ is hydrogen or an alkyl group having about 1 toabout 18 carbon atoms.
 2. A composition formed by contacting an olefinicpolymer containing an allylic hydrogen and having a molecular weightfrom about 500 to 10,000,000 with an acyclic carbonyl of the formula:

wherein Q is HOH, MeOH, EtOH or n-BuOH; n is 0,1 or >1; W is selectedfrom the group consisting of: —OH, —OR₁ and —NR₁R₂; V is selected fromthe group consisting of —R₂, —CH₂COOH, —CH₂COOR₁, —C(═O)COOH,—C(═O)COOR₁ and —C(═O)R₂; wherein R₁ is an alkyl group having about 1 toabout 18 carbon atoms, and R₂ is hydrogen or an alkyl group having about1 to about 18 carbon atoms.